Preparation of perfluoroolefins



United States Patent [mail 3,17fil3 as W. clhrook and @gdcn 7 in m, assiguors to Bow Co ning Corporation, h iidlsnd, h a corporation oi Michigan No mowing. Filed May 21, E52, der. No. 196,512

6 Claims. (til. see -seas;

It is an object of the present invention to provide a new method of preparing pertluoroalkenes.

Another object of this invention is to provide a method for preparing perfluoroalkenes that is simpler than prior methods.

A further object is to provide a one-step synthesis of perfluoroalkenes.

Still another object is to provide a method for producing periluoroolefins having an internal double bond.

hese and other objects will be apparent from the following description.

This invention relates to a method of preparing perfluoroolefins which method comprises reacting (l) a perhalocarbon of the formula CFX (CPX) CFXCFX wherein X is selected from the group consisting of chicrine and bromine, and n is a positive integer, with (2) an alkali metal fluoride wherein the alkali metal atom is selected from the group consisting of potassium, rubidium and cesium, under substantially anhydrous condition in (3) an inert or anic Liquid having a dielectric constant of at least until the hologen atoms other than fluorine have all been replaced with fluorine to give an internal perfiuoroolefin having the same number of carbon atoms per molecule as perhalocarbon (l).

The compounds convertible by the method of this invention to the desired products can be any alkane containin four or more carbon atoms per molecule, as de fined above. The compounds can be chlorotluorocarbons, bromoi'luorocarbons or chlorobromofiuorocarbons. EX- amples of alkane operable in the process of this invention include CF-Cl CFClCFBrCFBrCl, CFCl CFCl) CF C1 CFClBr(CFCl) CFBr CFBr (CF Br) C1 Br etc.

Many of the compounds described are available in commerce. Often these are materials that find no commercial use per se, so that the method of the present invention serves to convert these otherwise valueless com pounds to higldy useful materials.

The alkali metal fluoride can contain potassium, rubidium or cesium atoms therein. in addition to individual alkali metal fluorides, mixtures can also be employed. A preferred catalyst is potassium fluoride on account of its lower cost and greater availability, but any of the three or mixtures thereof will function herein.

The alkali metal fluoride is the source of fluorine atoms in the process of the invention, and thus should be supplied in sufficient amount to provide the needed fluorine atoms. If less than the minimum amount of alkali metal fluoride is supplied to the reaction of the yield of periuoroalkene will be reduced, and in addition some incompletely fluorinated compounds will result. However, should the above result, more alkali metal fluoride can be supplied to complete the desired reaction so that an initially incomplete amount of the inorganic fluoride is not ermanently deleterious to the process, in that the reaction only proceeds part way (on average), but can be completed by the further addition of fluorination agent. An excess over the minimum amount of alkali metal fluoride can of course be employed, but this is not necessary to the reaction. While small excesses (up to 50 per cent or so) may at times increase the rate of conversion, large excesses are wasteful of the alkali fluoride reagent.

it is convenient, but not necessary, to employ the alkali metal fluoride in finely divided form. Since the alkali metal fluoride should be used in a substantially anhydrous state, however, it is convenient to dry the salt when it is finely divided. Thus, the preferred condition of the alkali metal fluoride is finely divided. As well, any reaction involving a solid and a fluid is made more efficient when the solid is finely divided, in that more solid surface is exposed. Of course, when an organic liquid is ernployed that is a solvent for the alkali metal fluoride, its state of division is immaterial.

It is desirable to operate at a temperature at least high enough to achieve a practical rate of reaction. This temperature will ordinarily be at least about C. Temperatures above this minimum up to about 306 C. can be employed, limited only by the decomposition temperatures of the reactants and products. It is often advantageous to operate at temperatures of to 200 C. to obtain a desirably rapid rate of reaction when the starting material is relatively slow in reactin Reaction times at the stated temperature ranges will vary according to starting material, etc from as little as one hour or less to more than 8 hours for the desired conversions. Since upon further fluorination the organic compound acquires a lower boiling point, it is often useful to operate at a temperature between the boiling point of the reactant and that of the product.

The reaction can be conducted at atmospheric pressure, or higher or lower, depending on the reactants and desired operating temperature. Whenever possible it is of course easier to operate at atmospheric pressure, as this simplifies the equipment requirements. But pressures difierent from atmospheric can be employed where it is desired.

Both the rate of conversion and degree of conversion are quite minimal in the absence of certain organic 1iquids. The presence of these liquids appear necessary to the reaction. Any organic liquid having a dielectric constant of 2G or greater and containing no active hydrogen are applicable for use as liquid media for this reaction. By active hydrogen is meant that form of hydrogen in a molecule that will evolve methane in the well known Zerewitinoll test, which active hydrogen is usually found attached to oxygen, nitrogen or sulfur in an organic compound. dielectric constant is usually measured at 2- C, or (if the liquid freezes above 20 C.) at its melting point.

The amount of the said organic liquid present in the reaction mixture is not critical. It need only be sufiicient to keep the mixture fluid and to insure contact between the reactants. In practice, the weight of the said liquid used is at least equal to the weight of alkali metal fluoride.

Examples of applicable organic liquids, all having a dielectric constant greater than 20, include aliphatic and aromatic nitriles such as acetonitrile, butyronitrile, adiponitrile, benzonitrile, and zylonitrile; organic nitro compounds such as nitrornethane, nitroethane, l-nitrobutane, 2-nitropentane, nitrobenzene, orthonitrotoluene, paranitrotoluene, l-chloro-Z-nitrobenzene, methyl-ortho-nitrobenzoate, and the like; organic sulfates and sulfones such as dimetbyl sulfate, diethyl sulfate, cyclic tetramethyl sulione, di-n-butyl sulfcne, ethylmethyl sulfone and ethylphenyl sultone; and di-N-substituted amides such as 3 N,N-dimethylformamide, N,N-diethylpropionarnide, N,N- ethylpropylbenzamide and the like. Preferred organic liquid media on account of their low cost and availability are N,N-dimethylformarnide and dimethylsulfone.

The reactants produce internal. perfluoroolefins in the process of this invention. By internal perfluoroolefin is meant one in which the double bond is not .connected to a terminal carbon atom. The formation of a perfluoroalkene from a perhaloalkane isentirely unexpected by the use of alkali metal fluorides. It is probably due to a dehalogenation proceeding concurrent with the fluorination, but only internal perfluoroolefins are formed. The exact mechanism that produces only these olefins is not known at this time.

The process of the instant invention is further distinctive from many other fluorination'methods in that the process appears to be free of carbon-to-carbon bond cleavage. Thus, for example, a C reactant produces a C perfluoroolefin in good yield.

The following examples areillustrative only and should not be construed as limiting the invention which is properly delineated in the appended claims.

Example 1 A 0.5 mol (212.8 g.) portion of CFCl CFClCFBrCPClBr Example 2 A mixture of 66.5 g. (0.25 mo1) of CFCl CFClCF=CFCl 58.1 g. (1.0 mol) of potassium fluoride and 250 ml. of dimethylformamide were heated in a flask at 105 to 110 C. for a total of 19 hours. tilled out of the reaction vessel into a Dry Ice acetone cooled receiver, essentially all of it in the first three hours of reaction. Analysis of the 46 g. (92 percent yield) showed it to be pure CF CF=CFCF 95 percent the trans-isomer.

' Example 3 .A mixture of 0.166 mol(56.1 g.) of

CFCl CFClCFClCFCl 1.0 mol (58.1 g.) of potassium fluoride and about 200 g. of dimethylsulfone was heated in a flask to 195 C. for about 4 hours. receiver cooled to 80 F. A total of 13 g. (45 percent yield) of pure CF CF=CFCF was obtained.

A volatile product dis The volatile product was trapped in a 4 Example 4 Example 5 Equivalent results are obtained when either rubidium fluoride, cesium fluoride or a mixture of both is substituted for the potassium fluoride of Example 1.

Example 6 When any of the perhalocarbons shown in the table below are substituted for the perhalocarbon of Example 2 and the amount of potassium fluoride adjusted to provide the required fluorine, internal olcfins as shown are formed:

Perhaloearbon Product OFGlBrOFClCFBrCFOl OF3CF=CFOF OFB12(OFBI)GGFBY2 osFra That which is claimed is:

l. A method of preparing perfluoro-olefins which method comprises reacting (1) a perhalocarbon of the formula CFX (CFX) CFXCFX wherein X is selected from the group consisting of chlorine and bromine, and n isa positive integer, with (2) an alkali metal fluoride wherein the alkali metal atom is selected from the group consisting of potassium, rubidium and cesium, under substantially anhydrous conditions in (3) an inert organic liquid having a dielectric constant of at least 20 until the halogen atoms other than fluorine have all been replaced with fluorine to give an internal perfluoroolefln having the same number of carbon atoms per molecule as perhalocarbon (1). I

2. The method according to claim 1 wherein the alkali metal fluoride is potassium fluoride.

3. T he method according to claim 1 wherein the inert organic liquid is dimethylformamide.

4. The method according to claim'l wherein the inert organic liquid is dimethylsulfone. i

5. The method according to claim. 1 wherein for the perhalocarbon the value of n is 1.

6. The method according to claim ll wherein for the perhalocarbon n is 3. I

References Cited by the Examiner UNITED STATES PATENTS 2,842,603 *7/58 Miller 260-6533 2,918,501 12/59 Brehm et al. 260-653.3

3,024,290 3/62 Henne 260+653.3

JOSEPH R. LIBERMAN, Primary Examiner.

LEON ZITVER, Examiner. 

1. A METHOD OF PREPARING PERFLUORO-OLEFINS WHICH METHOD COMPRISES REACTING (1) A PERHALOCARBON OF THE FORMULA CFX2(CFX)NCFXCFX2 WHEREIN X IS SELECTED FROM THE GROUP CONSISTING OF CHLORINE AND BROMINE, AND N IS A POSITIVE INTEGER, WITH (2) AN ALKALI METAL FLUORIDE WHEREIN THE ALKALI METAL ATOM IS SELECTED FROM THE GROUP CONSISTING OF POTASSIUM, RUBIDUM AND CESIUM, UNDER SUBSTANTIALLY ANHYDROUS CONDITINS IN (3) AN INERT ORGANIC LIQUID HAVING A DIELECTRIC CONSTANT OF AT LEAST 20 UNTIL THE HALOGEN ATOMS OTHER THAN FLUORINE HAVE ALL BEEN REPLACED WITH FLUORINE TO GIVE AN INTERNAL PERFLUOROOLEFIN HAVING THE SAME NUMBER CARBON ATOMS PER MOLECULE AS PERHALOCARBON (1). 